DE2950096A1 - Beta-fluoroalkyl carbonate(s) prepn. - by reacting beta-fluoro:alkanol with carbon mon:oxide in presence of palladium catalyst, oxygen and manganese contg. redox co-catalyst - Google Patents

Beta-fluoroalkyl carbonate(s) prepn. - by reacting beta-fluoro:alkanol with carbon mon:oxide in presence of palladium catalyst, oxygen and manganese contg. redox co-catalyst

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DE2950096A1
DE2950096A1 DE19792950096 DE2950096A DE2950096A1 DE 2950096 A1 DE2950096 A1 DE 2950096A1 DE 19792950096 DE19792950096 DE 19792950096 DE 2950096 A DE2950096 A DE 2950096A DE 2950096 A1 DE2950096 A1 DE 2950096A1
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beta
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John Edward Hallgren
William Edward Smith
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General Electric Co
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General Electric Co
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    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract

beta-fluoroalkylcarbonates are made by reacting a beta-fluoroalkanol with carbon monoxide under anhydrous conditions in the presence of Pd, O2 and a Mn-contg. redox co-catalyst. The reaction may also be carried out in the presence of a base, a phase transfer agent and a drying agent such as a molecular sieve. Suitable Pd catalysts are palladium oxide, -nitrate, -sulphate, -oxalate, -acetate, -chloride, etc., or complexes such as Pd(CO)Cl2 2. The Mn cocatalyst has ligands chosen e.g. from omega-hydroxyoximes, alpha-diketones, beta-diketones, etc.; a specific cocatalyst is Mn(II)tris(acetylacetonate. The reaction is carried out e.g. at 0-200 degrees C, esp. 0-50 degrees C under a CO pressure of 0.5-500 atmos., esp. 1-200 atmos.

Description

Verfahren zur Herstellung von ß-FluoralkylcarbonatenProcess for the preparation of ß-fluoroalkyl carbonates

Die Erfindung betrifft ein Verfahren zur Herstellung von ß-Fluoralkylcarbonaten (ß-Fluoralkylkohlensäureester).The invention relates to a process for the preparation of β-fluoroalkyl carbonates (ß-Fluoroalkyl carbonic acid ester).

Die Synthese von Bis-(2,2,2-trifluoräthyl)-carbonat durch Reaktion von B-Trifluoräthanol mit Phosgen ist von Aldrich und Shepard in J. Org.Chem. 29, 11 (1964) beschrieben.The synthesis of bis (2,2,2-trifluoroethyl) carbonate by reaction of B-trifluoroethanol with phosgene is from Aldrich and Shepard in J. Org.Chem. 29 11 (1964).

Die vorliegende Erfindung schafft nunmehr ein Verfahren bei dem ein ß-Fluoralkanol mit Kohlenmonoxid in Anwesenheit einer Palladiumverbindung, Sauerstoff und einem Mangan-Redox-Cokatalysator unter wasserfreien Bedingungen unter Bildung eines ß-Fluoralkylcarbonats umgesetzt werden.The present invention now provides a method in which a ß-Fluoroalkanol with carbon monoxide in the presence of a palladium compound, oxygen and a manganese redox cocatalyst under anhydrous conditions to form a ß-fluoroalkyl carbonate are implemented.

Die Reaktionsbestandteile und die erhaltenen Reaktionsprodukte des Verfahrens können durch die nachfolgende Gleichung veranschaulicht werden, die indessen lediglich zur Erläuterung angeführt wird, da die betroffenen Reaktionsbestandteile, die Reaktionsprodukte und der Reaktionsmechanismus bei der Herstellung der ß-fluoraliphatischen Carbonate unterschiedlich und/oder wesentlich komplexer sein können: (I) 2CF3CH20H + CO + 1/2 0Katalysator, (CF3CH20 )2CO + H20. The reaction constituents and the resulting reaction products of the process can be illustrated by the following equation, which, however, is only given for explanation, since the reaction constituents concerned, the reaction products and the reaction mechanism in the preparation of the ß-fluoroaliphatic carbonates can be different and / or significantly more complex : (I) 2CF3CH20H + CO + 1/2 0 catalyst, (CF3CH20) 2CO + H20.

Der B-Fluoralkanol-Reaktionsbestandteil kann 2 bis 10 Kohlenstoffatome, vorzugsweise 2 bis 4 Kohlenstoffatome enthalten.The B-fluoroalkanol reaction component can have 2 to 10 carbon atoms, preferably contain 2 to 4 carbon atoms.

Beispiele solcher ß-Fluoralkanole sind die folgenden: CH2FCH2OH, CHF2CH2OH, CF3CH2OH, (CF3)2CHOH, CF3CF2CH2OH, CF3CHOH und CH3 CF3CF2CF2CH2OH.Examples of such ß-fluoroalkanols are the following: CH2FCH2OH, CHF2CH2OH, CF3CH2OH, (CF3) 2CHOH, CF3CF2CH2OH, CF3CHOH and CH3 CF3CF2CF2CH2OH.

Die Palladiumverbindung kann in Form einer anorganischen oder organischen Verbindung oder eines Komplexes vorliegen. Die Verbindungen umfassen das Oxid, das Halogenid, das Nitrat, das Sulfat, das Oxalat, das Acetat, das Carbonat, das Propionat, das Hydroxid und das Tartrat. Palladiumkomplexe mit Kohlenmonoxid, Nitrilen, tert. Aminen, Phosphinen, Arsinen oder Stibinen können Verwendung finden.The palladium compound can be in the form of an inorganic or organic Compound or a complex are present. The compounds include the oxide, the Halide, nitrate, sulfate, oxalate, acetate, carbonate, propionate, the hydroxide and the tartrate. Palladium complexes with carbon monoxide, nitriles, tert. Amines, phosphines, arsines or stibines can be used.

Beispiele der Palladiumverbindungen und -komplexe sind die folgenden: PdCl2, PdBr2, PdJ2, [Pd(CO)Cl2]2, [Pd(CO)Br2]2, [Pd(Co)J2]2, (C6H5CN)2PdCl2, Pd(OH)2(CNC4Hg)2, PdJ1 (CNC6 Hg ) Pd(OH)2-(CNCH3OC6H5)2, Pd(CNC4H9)41 Pd<CO)Cl, Pd(CO)J, PdH(CO)Cl, Pd(CO)Br, PdH(CO)Br., Pd(C6H6) (H20)C104, Pd2(C0)2Cl, (H9C4)4N72r4 K2Pd2(C0)2Cl und Na2Pd2(CO)2Br4.Examples of the palladium compounds and complexes are as follows: PdCl2, PdBr2, PdJ2, [Pd (CO) Cl2] 2, [Pd (CO) Br2] 2, [Pd (Co) J2] 2, (C6H5CN) 2PdCl2, Pd (OH) 2 (CNC4Hg) 2, PdJ1 (CNC6 Hg) Pd (OH) 2- (CNCH3OC6H5) 2, Pd (CNC4H9) 41 Pd <CO) Cl, Pd (CO) J, PdH (CO) Cl, Pd (CO) Br, PdH (CO) Br., Pd (C6H6) (H20) C104, Pd2 (C0) 2Cl, (H9C4) 4N72r4 K2Pd2 (C0) 2Cl and Na2Pd2 (CO) 2Br4.

Sauerstoff wird als einziges Oxidationsmittel in Kombination mit einem Redox-Cokatalysator verwendet, der ausgewählt ist aus Manganchelaten. Beispiele der Mangan-Redox-Cokatalysatoren sind Manganchelate, welche Liganden enthalten, die ausgewählt sind aus omega () -Hydroxyoximen, ortho(o)-Hydroxyarelloximen, alpha-( )-Diketon- oder beta(ß) -Diketonliganden einschließlich Kombinationen derselben. Typische Beispiele von wohl bekannten im Handel erhältlichen Redox-Cokatalysatoren umfassen Mangan(II)-bis-(acetylacetonat), Mangan(II)-bis-(benzoinoxim) usw. Die Redox-Cokatalysatoren sind dem Fachmann wohlbekannt und können aufgrund der Offenbarungen in den US-Patenten 3 972 851, 3 965 069, 3 956 242, 3 781 382, 3 455 880 und 3 444 133 leicht hergestellt werden.Oxygen is used as the only oxidizer in combination with a Redox cocatalyst used, which is selected from Manganese chelates. Examples of manganese redox cocatalysts are manganese chelates, which contain ligands, which are selected from omega () -hydroxyoximes, ortho (o) -hydroxyarelloximes, alpha- ( ) -Diketone or beta (ß) -diketone ligands including combinations thereof. Typical examples of well known commercially available redox cocatalysts include manganese (II) -bis- (acetylacetonate), manganese (II) -bis- (benzoinoxime), etc. The Redox cocatalysts are well known to the person skilled in the art and can based on the disclosures U.S. Patents 3,972,851, 3,965,069, 3,956,242, 3,781,382, 3,455,880, and 3,444 133 can be easily made.

Das Verfahren kann in Abwesenheit eines Lösungsmittels durchgeführt werden, beispielsweise, wenn der ß-Fluoralkanol-Reaktionsbestandteil sowohl als Lösungsmittel als auch als Reaktionsbestandteil wirkt. Repräsentative Beispiele für Lösungsmittel, die verwendet werden können,sind: Methylenchlorid, Äthylendichlorid, Chloroform, Kohlenstofftetrachlorid, Tetrachloräthylen, Nitromethan, Hexan, 3-Methylpentan, Heptan, Cyclohexan, Methylcyclohexan, Cyclohexan, Isooctan, p-Cymol (Isopropyl-p-methylbenzol), Decalin, Toluol, Benzol, Diphenyläther, Dioxan, Thiophen, Dimethylsulfid, Äthylacetat, Tetrahydrofuran, Chlorbenzol, Anisol, Brombenzol, o-Dichlorbenzol, Methylformiat, Jodbenzol, Aceton und Acetophenon sowie Mischungen derselben.The process can be carried out in the absence of a solvent be, for example, when the ß-fluoroalkanol reactant both as Solvent acts as a reaction component as well. Representative examples for solvents that can be used are: methylene chloride, ethylene dichloride, Chloroform, carbon tetrachloride, tetrachlorethylene, nitromethane, hexane, 3-methylpentane, Heptane, cyclohexane, methylcyclohexane, cyclohexane, isooctane, p-cymene (isopropyl-p-methylbenzene), Decalin, toluene, benzene, diphenyl ether, dioxane, thiophene, dimethyl sulfide, ethyl acetate, Tetrahydrofuran, chlorobenzene, anisole, bromobenzene, o-dichlorobenzene, methyl formate, Iodobenzene, acetone and acetophenone and mixtures thereof.

Obgleich nicht erforderlich, so kann das Verfahren doch unter basischen Reaktionsbedingungen ausgeführt werden. Repräser,tative Beispiele der Basen, die hierfür verwendet werden können, sind die folgenden: Elementare Alkali- und Erdalkalimetalle, basische quaternäre Ammonium-, quaternäre Phosphonium-oder tert. Sulfoniumverbindungen; Alkali- oder Erdalkalimetallhydroxide; Salze starker Basen und schwacher organischer Säuren; primäre, sekundäre oder tertiäre Amine; usw. Spezielle Beispiele der vorerwähnten Stoffe sind: Natrium-,Kalium-, Magnesiummetalle usw.; quaternäres Ammoniumhydroxid, Tetraäthylphosphoniumhydroxid usw.; Natrium-, Kalium-, Lithium- und Calciumhydroxid; quaternäres Phosphonium, tertiäres Sulfonium, Natrium-, Lithium- und Bariumcarbonat, Natriumacetat, Natriumbenzoat, Natriummethylat, Natriumthiosulfat, Natriumverbindungen, beispielsweise das Sulfid, Tetrasulfid, Cyanid, Hydrid und Borhydrid; Kaliumfluorid, Methylamin, Isopropylamin, Methyläthylamin, Allyläthylamin, Ditert.-Butylamin, Dicyclohexylamin, Dibenzylamin, tert-Butylamin, Allyldiäthylamin, Benzyldimethylamin, Diacetylchlorbenzylamin, Dimethylphenyläthylamin, 1-Dimethylamino-2-phenylpropan, Propandiamin, Äthylendiamin, N-Methyläthylendiamin, N,N' -Dimethyläthylendiamin, N,N,N'-Tri-tert.-butylpropandiamin, N,N',N',N"-Tetramethyldiäthylentriamin, Pyridin, Aminomethylpyridine, Pyrrol, Pyrrolidin, Piperidin, 1,2,2,6,6-Pentamethylpiperidin und Imidazol. Besonders bevorzugte Basen72ie Hydroxide von Lithium, Natrium, Kalium, Calcium oder Barium; Natrium-, Lithium-oder Bariumcarbonat; Natriumacetat, Natriumbenzoat, Natriummethylat usw. einschließlich Mischungen derselben.Although not required, the process can be carried out under basic Reaction conditions are carried out. Representative examples of the bases that The following can be used for this: Elemental alkali and alkaline earth metals, basic quaternary ammonium, quaternary phosphonium or tert. Sulfonium compounds; Alkali or alkaline earth metal hydroxides; Salts of strong bases and weak organic ones Acids; primary, secondary or tertiary amines; etc. Specific examples of the aforementioned Substances are: sodium, potassium, magnesium metals etc .; quaternary ammonium hydroxide, Tetraethylphosphonium hydroxide, etc .; Sodium, potassium, lithium and calcium hydroxide; quaternary Phosphonium, tertiary sulfonium, sodium, lithium and barium carbonate, sodium acetate, sodium benzoate, sodium methylate, sodium thiosulfate, Sodium compounds, for example the sulfide, tetrasulfide, cyanide, hydride and Borohydride; Potassium fluoride, methylamine, isopropylamine, methylethylamine, allylethylamine, Di-tert-butylamine, dicyclohexylamine, dibenzylamine, tert-butylamine, allyl diethylamine, Benzyldimethylamine, diacetylchlorobenzylamine, dimethylphenylethylamine, 1-dimethylamino-2-phenylpropane, Propanediamine, ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, N, N, N'-tri-tert.-butylpropanediamine, N, N ', N', N "-tetramethyl diethylenetriamine, pyridine, Aminomethylpyridines, pyrrole, pyrrolidine, piperidine, 1,2,2,6,6-pentamethylpiperidine and imidazole. Particularly preferred bases, hydroxides of lithium, sodium, potassium, Calcium or barium; Sodium, lithium or barium carbonate; Sodium acetate, sodium benzoate, Sodium methylate, etc. including mixtures thereof.

Obgleich nicht erforderlich, so kann das Verfahren doch in Gegenwart eines organischen Phasenübergangsmittels durchgeführt werden, wobei beliebige Oniumphasenübergangsmittel umfaßt werden, z.B.Although not required, the process can be performed in the presence an organic phase change agent, with any onium phase change agent be included, e.g.

quaternäres Ammoniumhydroxid und Tetraäthylphosphoniumhydroxid, wie sie von C.M. Starks in J.A.C.A. 93, 195 (1971) beschrieben sind; Kronenäther-Phasenübergangsmittel, wie sie beispielsweise von G.W. Gokel und H.D. Durst in Aldrichimica Acta 9, Ausgabe Nr. 1 (Ausgabe 1976) "Crown Ether Chemistry: Principles and Applications" sowie von C.J. Pederson im US-Patent 3 622 577 beschrieben sind,sowie beliebige kationische Salze, z.B. Alkali-oder Erdalkalimetalldiaminhalogenide; und Kryptate.quaternary ammonium hydroxide and tetraethylphosphonium hydroxide, such as she by C.M. Starks in J.A.C.A. 93, 195 (1971); Crown ether phase transfer agent, as described, for example, by G.W. Gokel and H.D. Thirst in Aldrichimica Acta 9, edition No. 1 (1976 edition) "Crown Ether Chemistry: Principles and Applications" and by C.J. Pederson in U.S. Patent 3,622,577, as well as any cationic Salts, e.g., alkali or alkaline earth metal diamine halides; and cryptates.

Die Molverhältnisse von Palladium zu ß-Fluoralkanol liegen im Bereich von 0,001 : 1 bis 1000 : 1, vorzugsweise von 0,1 : 1 bis 10 : 1.The molar ratios of palladium to ß-fluoroalkanol are in the range from 0.001: 1 to 1000: 1, preferably from 0.1: 1 to 10: 1.

Wenn eine Base verwendet wird, dann liegt das effektive Molverhältnis von Base zu Palladium im Bereich von 0,000001 : 1 bis 100 : 1, vorzugsweise von 0,5 : 1 bis etwa 10 : 1 und mehr bevorzugt von 1 : 1 bis 2 : 1.If a base is used then the effective molar ratio is from base to palladium in the range of 0.000001: 1 to 100: 1, preferably from 0.5: 1 to about 10: 1 and more preferably from 1: 1 to 2: 1.

Das Molverhältnis von Oxidationsmittel zu ß-Fluoralkanol kann im Bereich von 0,001 : 1 bis etwa 1000 : 1, vorzugsweise von 0,1 :1 bis 10 : 1 liegen.The molar ratio of oxidizing agent to ß-fluoroalkanol can be in the range from 0.001: 1 to about 1000: 1, preferably from 0.1: 1 to 10: 1.

Das Molverhältnis von Redoxkatalysator zu ß-Fluoralkanol liegt im Bereich von 0,0001: 1 bis 1000 : 1, vorzugsweise von 0,0001 1 bis 1 : 1 und mehr bevorzugt im Bereich von 0,001 : 1 bis 0,01 : 1.The molar ratio of redox catalyst to ß-fluoroalkanol is in Range from 0.0001: 1 to 1000: 1, preferably from 0.0001: 1 to 1: 1 and more preferably in the range from 0.001: 1 to 0.01: 1.

Das Molverhältnis von Phasenübergangsmittel zu Palladium kann im Bereich von 0,00001 : 1 bis 1000 : 1, vorzugsweise von 0,05 1 bis 100 : 1 und mehr bevorzugt im Bereich von 10 : 1 bis 20 : 1 liegen.The molar ratio of phase change agent to palladium can be in the range from 0.00001: 1 to 1000: 1, preferably from 0.05 1 to 100: 1 and more preferably range from 10: 1 to 20: 1.

Das Verfahren wird vorzugsweise unter einem positiven Kohlenmonoxiddruck durchgeführt in Mengen, die ausreichen, um das gewünscht B-fluoraliphatische Carbonat zu bilden, im allgemeinen in einem Druckbereich von etwa 1/2 bis etwa 500 at, vorzugsweise in einem Druckbereich von 1 bis 200 at.The process is preferably carried out under a positive carbon monoxide pressure carried out in amounts sufficient to produce the desired B-fluoroaliphatic carbonate generally in a pressure range of about 1/2 to about 500 atmospheres, preferably in a pressure range from 1 to 200 at.

Allgemein liegen optimale Reaktionstemperaturen im Bereich von OOC bis 2000C, vorzugsweise von OOC bis 500C.In general, optimal reaction temperatures are in the OOC range to 2000C, preferably from OOC to 500C.

In den nachfolgenden Beispielen wurden alle Reaktionsprodukte durch gaschromatografische Massenspektrometrie nachgewiesen.In the following examples, all reaction products were through gas chromatographic mass spectrometry detected.

Beispiel 1 Ein 50 ml-Dreihalskolben, der mit unter die Oberfläche reichenden Luft- und eO-Einlaßrohren versehen war, wurde nit 1 0 g (10 mMol) 2,2,2-Trifluoräthanol (CF3CH2OH), 0,027 g (0,1 mZbl} PdBr2, 0,106 g (0,3 mMbl) Nangantri(acetylacetonat) (MnXacac33), 0,23 g (1,5 mMol) 1,2,2,6,6-Pentamethylpiperidin, 2 g Molekularsiebe vom Typ Linde 3A und 25 ml Methylenchlorid beschickt 100,0 µl Toluol als ein innerer Standard und CO und Luft wurden 16 Std. lang bei einer Temperatur von 250C durch die Mischung h indurchpe rlen gelassen. Die Dampfphasenchromatografie (Vpc) zeigte die Anwesenheit von 0,74 g (67 %-ige Umwandlung) Bis-(2,2,2-trifluoräthyl)-carbonat mit der Formel: (CF3CH20 )2CO.Example 1 A 50 ml three-necked flask that goes under the surface was provided with air and eO inlet tubes, was nit 10 g (10 mmol) of 2,2,2-trifluoroethanol (CF3CH2OH), 0.027 g (0.1 mZbl} PdBr2, 0.106 g (0.3 mMbl) nangan tri (acetylacetonate) (MnXacac33), 0.23 g (1.5 mmol) 1,2,2,6,6-pentamethylpiperidine, 2 g molecular sieves Linde 3A type and 25 ml of methylene chloride charged 100.0 µl of toluene as an internal Standard and CO and air were passed through for 16 hours at a temperature of 250C let the mixture flow through. Vapor phase chromatography (Vpc) showed the presence of 0.74 g (67% conversion) of bis (2,2,2-trifluoroethyl) carbonate with the formula: (CF3CH20) 2CO.

Beispiel II Ein 50 ml-Dreihalskolben, der mit unter die Oberfläche ragenden Luft- und CO-Einlaßrohren versehen war, wurde mit 32,2 g (0,322 mMol) CF3CH2OH, 0,027 g (0,1 mMol) PdBr2, 0,106 g (0,3 mMol) Mn(acac)3, 0,232 g (1,5 mMol) 1,2,2,6,6,-Pentamethylpiperidin und 2 g Molekularsiebe vom Typ Linde 3A beschickt. CO und Luft wurden 16 Std. lang durch die Mischung perlen gelassen. Die Dampfphasenchromatografie (Vpc) zeigte die Anwesenheit von 0,44 g Bis-(2,2,2-trifluoräthyl)-carbonat.Example II A 50 ml three-necked flask that goes below the surface protruding air and CO inlet pipes was provided with 32.2 g (0.322 mmol) CF3CH2OH, 0.027 g (0.1 mmol) PdBr2, 0.106 g (0.3 mmol) Mn (acac) 3, 0.232 g (1.5 mmol) 1,2,2,6,6-pentamethylpiperidine and charged 2 g of Linde 3A molecular sieves. CO and air were for 16 hours bubbled through the mixture. Vapor phase chromatography (Vpc) showed the Presence of 0.44 g of bis (2,2,2-trifluoroethyl) carbonate.

Beispiel III Ein 100 ml-Dreihalskolben, der mit unter die Oberfläche ragenden Luft- und CO-Einlaßrohren versehen war, wurde mit 3,8 g (38 mMol) CF3CH2OH, 0,027 g (0,1 mMol) PdBr2, 0,106 g (0,3 mMol) Mn(acac)3, 2 g Molekularsieben vom/inde 3A und 50 ml Methylenchlorid beschickt. CO und Luft wurden dann 42 Std. lang durch die Mischung perlen gelassen. Die Dampfphasenchromatografie (Vpc) zeigte die Anwesenheit von 0,26 g Bis-(2,2,2-trifluoräthyl)-carbonat.Example III A 100 ml three-necked flask that goes below the surface protruding air and CO inlet pipes was provided, 3.8 g (38 mmol) of CF3CH2OH, 0.027 g (0.1 mmol) of PdBr2, 0.106 g (0.3 mmol) of Mn (acac) 3, 2 g of inde molecular sieves 3A and 50 ml of methylene chloride charged. CO and air were then passed through for 42 hours let the mixture pearl. Vapor phase chromatography (Vpc) showed the presence of 0.26 g of bis (2,2,2-trifluoroethyl) carbonate.

Beispiel IV Ein 100 ml-Dreihalskolben, der mit CO-Einlaß- und Luftauslaßrohr und einem Rührstab versehen war, wurde mit 1,28 g (12,8 mMol) CF3CH2OH, 0,104 g (1,3 mMol) 50 %-iger wässriger Natronlauge (NaOH), 0,37 g (1,6 mMol) Tetrabutylammoniumbromid (Bu4N Br ), 2,0 g der Molekularsiebe und 70 ml Methylenchlorid beschickt. Die Mischung wurde bei Raumtemperatur 1 Std. gerührt, dann wurden 0,076 g (0,3 mMol) Mn(acac)2 und 0,27 g (0,1 mMol) PdBr2 zugegeben. CO und Luft wurden bei Raumtemperatur dann weitere 18 Std. lang durch die Mischung perlen gelassen. Die Dampfphasenchromatografie (Vpc) zeigte die Anwesenheit von 0,94 g (73 %-ige Umwandlung) des Bis-(2,2,2-trifluoräthyl) -carbonats.Example IV A 100 ml three neck flask fitted with CO inlet and air outlet tubes and a stir bar was added with 1.28 g (12.8 mmol) CF3CH2OH, 0.104 g (1.3 mmol) 50% aqueous sodium hydroxide solution (NaOH), 0.37 g (1.6 mmol) tetrabutylammonium bromide (Bu4N Br), 2.0 g of the molecular sieves and 70 ml of methylene chloride. The mixture was stirred at room temperature for 1 hour, then 0.076 g (0.3 mmol) of Mn (acac) 2 and 0.27 g (0.1 mmol) of PdBr2 were added. CO and air were then at room temperature Let the mixture bubble for an additional 18 hours. The vapor phase chromatography (Vpc) showed the presence of 0.94 g (73% conversion) of the bis (2,2,2-trifluoroethyl) carbonate.

Beispiel V Ein 100 ml-Dreihalskolben, der mit CO-Einlaß-, Lufteinlaß, -auslaßrohr und Rührstab versehen war, wurde mit 40 ml CF3 -CH2OH, 0,104 g (1,3 mMol) 50 %-ige wässrige Lauge und 3,0 g Molekularsieb beschickt. Die Mischung wurde dann bei Raumtemperatur 1 Std. gerührt, dann 0,027 g (o,1 mMol) PdBr2 und 0,076 g (0,3 mMol) Mn(acac)2 beschickt. CO und Luft wurden langsam 18 weitere Std. lang durch die Reaktionsmischung hindurchperlen gelassen. Die Dampfphasenchromatografie (Vpc) zeigte die Anwesenheit von 8,45 g (16,4 %-ige Umwandlung) des Bis-(trifluoräthyl)-carbonats.Example V A 100 ml three-necked flask fitted with CO inlet, air inlet, outlet tube and stir bar, 40 ml CF3 -CH2OH, 0.104 g (1.3 mmol) 50% aqueous alkali and 3.0 g molecular sieve charged. The mix was then stirred at room temperature for 1 hour, then 0.027 g (0.1 mmol) of PdBr2 and 0.076 g (0.3 mmol) of Mn (acac) 2 charged. CO and air were slowly increasing for 18 more hours bubbled through the reaction mixture. The vapor phase chromatography (Vpc) indicated the presence of 8.45 g (16.4% conversion) of the bis (trifluoroethyl) carbonate.

Claims (9)

Patentansprüche t Verfahren zur Herstellung von ß-Fluoralkylcarbonaten, dadurch gekennzeichnet, daß ein ß-Fluoralkanol mit Kohlenmonoxid in Anwesenheit von Palladium, Sauerstoff und einem Mangan-Redox-Cokatalysator unter wasserfreien Bedingungen umgesetzt wird. Claims t process for the production of ß-fluoroalkyl carbonates, characterized in that a ß-fluoroalkanol with carbon monoxide in the presence of palladium, oxygen and a manganese redox cocatalyst under anhydrous Conditions is implemented. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß es in Anwesenheit einer Base durchgeführt wird. 2) Method according to claim 1, characterized in that it is in the presence a base is carried out. 3) Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es in Anwesenheit eines Phasenübergangsmittels durchgeführt wird. 3) Method according to claim 1 or 2, characterized in that it is carried out in the presence of a phase change agent. 4) Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß es in Anwesenheit eines Trocknungsmittels durchgeführt wird. 4) Method according to claim 1, 2 or 3, characterized in that it is carried out in the presence of a drying agent. 5) Verfahren nach Anspruch 4, dadurch gekennzeichnet daß das Trocknungsmittel ein Molekularsieb ist. 5) Method according to claim 4, characterized in that the drying agent is a molecular sieve. 6) Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Redox-Cokatalysator Mangan(II)-tri-(acetylacetonat) ist.6) Method according to one of the preceding claims, characterized in that that the redox cocatalyst is manganese (II) tri- (acetylacetonate). 7) Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das ß-Trifluoralkanol 2,2,2-Trifluoräthanol und der Palladiumkatalysator Palladium(II)-dibromid ist.7) Method according to one of the preceding claims, characterized in that that the ß-trifluoroalkanol is 2,2,2-trifluoroethanol and the palladium catalyst is palladium (II) dibromide is. 8) Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Base 1 ,2,2,6,6-Pentamethylpiperidin ist.8) Method according to claim 2, characterized in that the base 1,2,6,6-pentamethylpiperidine. 9) Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das Phasenübergangsmittel Tetraoutylammoniumbromid ist.9) Method according to claim 3, characterized in that the phase change agent Is tetraoutylammonium bromide.
DE19792950096 1978-12-15 1979-12-13 Beta-fluoroalkyl carbonate(s) prepn. - by reacting beta-fluoro:alkanol with carbon mon:oxide in presence of palladium catalyst, oxygen and manganese contg. redox co-catalyst Withdrawn DE2950096A1 (en)

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WO2001062702A1 (en) * 2000-02-22 2001-08-30 General Electric Company Method and catalyst system for producing aromatic carbonates
US6794988B1 (en) 1998-11-11 2004-09-21 Robert Bosch Gmbh Control device for a motor vehicle

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DE2738488A1 (en) * 1976-10-12 1978-04-13 Gen Electric PROCESS FOR THE PRODUCTION OF AROMATIC CARBONATES
DE2738487A1 (en) * 1976-10-12 1978-04-13 Gen Electric PROCESS FOR THE PRODUCTION OF AROMATIC CARBONATES

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Cited By (3)

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US6794988B1 (en) 1998-11-11 2004-09-21 Robert Bosch Gmbh Control device for a motor vehicle
WO2001062702A1 (en) * 2000-02-22 2001-08-30 General Electric Company Method and catalyst system for producing aromatic carbonates
US6380418B1 (en) 2000-02-22 2002-04-30 General Electric Company Catalyst compositions for producing aromatic carbonates

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